Deodorized polyether-modified polysiloxane composition, method for producing the same, and cosmetic containing the same

ABSTRACT

The deodorized, polyether-modified polysiloxane composition not producing a substance giving off a foul odor, while being produced or stored, which results from hydrolysis, oxidation or the like of a by-product or unreacted material and temporarily stable, a method for producing the same, and a cosmetic containing the same, wherein a polyether-modified polysiloxane composition, synthesized by hydrosilylation in which a polyoxyalkylene having the carbon-carbon double bond at the terminal is reacted with an organohydrogen polysiloxane, is refined by treatment in the presence of a solid acid.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a deodorized, polyether-modifiedpolysiloxane composition, method for producing the same and cosmeticcontaining the same, more particularly a deodorized, polyether-modifiedpolysiloxane composition not producing a substance giving off a foulodor, while being produced or stored, which results from hydrolysis,oxidation or the like of a by-product or unreacted material andtemporarily stable, and method for producing the same and cosmeticcontaining the same.

2. Description of the Prior Art

A polyether-modified polysiloxane is traditionally synthesized byhydrosilylation in which a polysiloxane having hydrosilyl group isreacted with a polyoxyalkylene having an unsaturated bond.

The polyether-modified polysiloxane, however, involves a disadvantage ofgiving off a foul odor with the lapse of time, making itself difficultto be used for cosmetics, e.g., those for the hair or skin.

This disadvantage was considered to result from deterioration of thepolyether-modified polysiloxane by oxidation which occurs with the lapseof time to form aldehyde. However, another cause is reported. Forexample, JP-A-2-302438 discusses that a foul odor results from anunreacted, propenyl-etherified polyoxyalkylene (refer to the claims orthe like). More specifically, part of an allyl-etherifiedpolyoxyalkylene is transformed into a propenyl-etherifiedpolyoxyalkylene because of its double bond migrating inwards in thepresence of a platinum catalyst while the polysiloxane compositionmodified with a polyether is being produced. As a result, it remainsunreacted with an organohydrogen polysiloxane to be left in thepolysiloxane composition modified with a polyether, and is decomposedwith the lapse of time into a ketone or aldehyde to give off a foulodor. The patent document also discloses that the composition can beeffectively deodorized by hydrolysis in the presence of an acid. Thisdeodorizing approach will be effective for removal of the unsaturatedgroup, when the allyl group in the residual polyoxyalkylene is totallytransformed into propenyl group. In actuality, however, theallyl-etherified polyoxyalkylene undergoing no rearrangement remains tosome extent to reduce the deodorizing effect, because the isomerizationin the presence of a platinum catalyst reaches an equilibrium. In otherwords, the approach disclosed by the above patent document involves aproblem of insufficient acid strength for hydrolysis of anallyl-etherified polyoxyalkylene.

Hydrolysis of an allyl-etherified polyoxyalkylene in the presence of astronger acid is not adequate, because of the possible scission of thecarbon-oxygen bond in the polyoxyalkylene or silicon-oxygen bond in thepolysiloxane.

Moreover, the hydrolysis needs excessive quantities of water and acid inorder to proceed quantitatively, which introduce greater complexity intothe post-treatment. Therefore, the above deodorization approach is notideal. Still more, the foul odor results not only from the carbon-carbondouble bond but also from unstable oxides or the like difficult toidentify. This is another problem involved in the above approach.

In consideration of the disadvantages involved in the deodorizationbased on the hydrolysis in the presence of an acid, varied solutionshave been proposed to control formation of odorous substances byhydrolysis, oxidation or the like of polyether-modified polysiloxane.For example, U.S. Pat. No. 5,225,509 discloses a method for deodorizinga polyoxyalkylene polysiloxane by hydrogenation under the conditions oftemperature: 20 to 200° C., pressure: 1 to 100 bars and reaction time:0.5 to 10 hours in the presence of a hydrogenation catalyst (refer tothe claims or the like). JP-A-7-330907, 9-165315 and 9-165318 disclosethat a polyether-modified polysiloxane composition, synthesized byhydrosilylation in which a polyoxyalkylene having the carbon-carbondouble bond at the terminal is reacted with an organohydrogenpolysiloxane, can be temporarily stable without giving off a foul odor,when hydrogenated (refer to the claims or the like).

However, the composition treated only by hydrogenation may still containan aldehyde condensate, e.g., acetal, which can be transformed into thealdehyde in an aqueous solution to cause foul odor. This is becausehydrogenation alone cannot sufficiently treat an aldehyde condensate,which lacks an unsaturated bond, to remove odorous substances.

In consideration of the above problems, WO-02/055588, for example,proposes a deodorized, modified silicone compound having a degree ofunsaturation and aldehyde formed each controlled at a specific level orless, and cosmetic containing the same, where the modified siliconecompound is refined by (A) hydrogenation of the residual unsaturatedbond and subsequent decomposition of an aldehyde condensate in anacid-containing, aqueous solution kept at a pH of 7 or less, or (B)decomposition of a propenyl-etherified product in an acid-containing,aqueous solution kept at a pH of 7 or less and subsequent hydrogenationof the aldehyde formed and residual unsaturated bond (refer to claims orthe like).

The above proposal, however, needs treatment in an acid-containing,aqueous solution kept at a pH of 7 or less as the essential step.Therefore, the acidic substance in the aqueous solution is dissolved andhence remains in the system. As a result, the acid treatment should begenerally followed by a neutralization step, and the salt formed by theneutralization also partly remains in the system. Thus, the aboveproposal involves the problems that the acid substance and salt by theneutralization remain in the system. In particular, a polyether-modifiedpolysiloxane is more hydrophilic than a dimethyl polysiloxane, andallows the acidic substance and salt by neutralization to remain in thesystem to a higher content. These residual substances cause anotherproblem of retarding the hydrogenation step, when it follows theneutralization step.

Moreover, a polyether-modified polysiloxane containing trace quantitiesof the acidic substance and salt by neutralization also involves aproblem of causing a foul smell of the system with the lapse of time,when it comprises water and a polyhydric alcohol, conceivably resultingfrom, e.g., the residual substances themselves or a decompositionproduct thereof, or a decomposition product of the polyether-modifiedpolysiloxane.

SUMMARY OF THE INVENTION

In consideration of the above problems, it is an object of the presentinvention to provide a deodorized, polyether-modified polysiloxanecomposition not producing a substance giving off a foul odor, whilebeing produced or stored, which results from hydrolysis, oxidation orthe like of a by-product or unreacted material, and temporarily stable.It is another object of the present invention to provide a method forproducing the same composition. It is still another object of thepresent invention to provide a cosmetic containing the same composition.

The inventors of the present invention have found, after havingextensively studied to solve the above problems, that a varyingpolyether-modified polysiloxane can be highly refined by hydrogenationwith a hydrogen gas in the presence of a catalyst and subsequenttreatment in the presence of a solid acid to produce a deodorized,polyether-modified polysiloxane composition not producing a substancegiving off a foul odor which results from hydrolysis, oxidation or thelike of a by-product or unreacted material, and temporarily stable. Theyhave investigated these findings to reach the present invention.

The first aspect of the present invention is a deodorized,polyether-modified polysiloxane composition, wherein apolyether-modified polysiloxane composition, synthesized byhydrosilylation in which a polyoxyalkylene having the carbon-carbondouble bond at the terminal is reacted with an organohydrogenpolysiloxane, is refined in the presence of a solid acid.

The second aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the first aspect, whereinthe polyether-modified polysiloxane composition is refined byhydrogenation, in addition to treatment in the presence of a solid acid.

The third aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the second aspect,wherein the polyether-modified polysiloxane composition is refined firstby hydrogenation and then by treatment in the presence of a solid acid.

The fourth aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the second aspect,wherein the polyether-modified polysiloxane composition is refined firstby treatment in the presence of a solid acid and then by hydrogenation.

The fifth aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the first aspect, whereinwater is incorporated in the treatment in the presence of a solid acid.

The sixth aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the first aspect, whereina lighter fraction is distilled off during or after the treatment in thepresence of a solid acid, or during or after the treatment byhydrogenation.

The seventh aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the first aspect, whereinthe solid acid is at least one selected from the group consisting ofsolid, acidic zirconium oxide, strongly acidic cation-exchanging resin,fluorinated sulfonic acid resin, acidic clay, alumina, silica-aluminaand zeolite.

The eighth aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the seventh aspect,wherein the solid acid is one of solid, acidic zirconium oxide andstrongly acidic cation-exchanging resin.

The ninth aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the eighth aspect,wherein the solid acid is solid, acidic zirconium oxide.

The tenth aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the seventh aspect,wherein the solid, acidic zirconium oxide is produced by a processinvolving kneading aluminum hydroxide and/or hydrous oxide, zirconiumhydroxide and/or hydrous oxide, and a compound containing sulfuric acid,forming the above mixture, and firing the formed product at atemperature at which zirconia of the tetragonal structure is produced.

The 11^(th) aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the first aspect, whereinthe polyether-modified polysiloxane composition contains at least oneselected from the group consisting of a compound represented by thegeneral formula (1):R¹ ₃SiO(R₂SiO)_(m)(RXSiO)_(n)SiR¹ ₃  (1)(wherein, Rs are each hydrogen atom, or a substituted or unsubstitutedmonovalent hydrocarbon group; “m” is 0 or a positive integer and “n” is0 or a positive integer; and X is a group represented by the generalformula:—C_(x)H_(2x)(OC₂H₄)_(y)(OC₃H₆)_(z)OA(wherein, A is hydrogen atom, or a group selected from the groupconsisting of a monovalent hydrocarbon group or one represented by theformula R²—(CO)— (R² is a monovalent hydrocarbon group); “x” is aninteger of 2 to 15, “y” is an integer of 0 to 100 and “z” is an integerof 0 to 100, “y+z” being an integer of 100 or less; and R¹ is a groupselected from the group consisting of R and X, at least one of R¹s beingX when “n” is 0), and the general formula (2):[(R₂SiO)_(m)R₂SiC_(x)H_(2x)(OC₂H₄)_(y)(OC₃H₆)_(z)OC_(x)H_(2x)]_(p)  (2)(wherein, Rs are each hydrogen atom, or a substituted or unsubstitutedmonovalent hydrocarbon group; “m” is a positive integer and “p” is aninteger of 1 to 100, “x” is an integer of 2 to 15, “y” is an integer of0 to 100 and “z” is an integer of 0 to 100, “y+z” being an integer of100 or less).

The 12^(th) aspect of the present invention is the deodorized,polyether-modified polysiloxane composition of the first aspect, whereinan antioxidant is incorporated.

The 13^(th) aspect of the present invention is a method for producing adeodorized, polyether-modified polysiloxane composition, comprising astep of treating a polyether-modified polysiloxane composition,synthesized by hydrosilylation in which a polyoxyalkylene having thecarbon-carbon double bond at the terminal is reacted with anorganohydrogen polysiloxane, in the presence of a solid acid.

The 14^(th) aspect of the present invention is the method of the 13^(th)aspect for producing a deodorized, polyether-modified polysiloxanecomposition, comprising a step of hydrogenation of thepolyether-modified polysiloxane composition, in addition to thetreatment in the presence of a solid acid.

The 15^(th) aspect of the present invention is the method of the 14^(th)aspect for producing a deodorized, polyether-modified polysiloxanecomposition, wherein the treatment in the presence of a solid acid iscarried out before or after the hydrogenation of the polyether-modifiedpolysiloxane composition.

The 16^(th) aspect of the present invention is the method of the 13^(th)aspect for producing a deodorized, polyether-modified polysiloxanecomposition, wherein a step for distilling off a lighter fraction iscarried out during or after the treatment in the presence of a solidacid, or before or after the treatment by hydrogenation.

The 17^(th) aspect of the present invention is the method of the 13^(th)aspect for producing a deodorized, polyether-modified polysiloxanecomposition, wherein the solid acid is at least one selected from thegroup consisting of solid, acidic zirconium oxide, strongly acidiccation-exchanging resin, fluorinated sulfonic acid resin, acidic clay,alumina, silica-alumina and zeolite.

The 18^(th) aspect of the present invention is the method of the 17^(th)aspect for producing a deodorized, polyether-modified polysiloxanecomposition, wherein the solid acid is one of solid, acidic zirconiumoxide and strongly acidic cation-exchanging resin.

The 19^(th) aspect of the present invention is a cosmetic containing thedeodorized, polyether-modified polysiloxane composition of one of thefirst to 12^(th) aspects.

As described above, the present invention relates to a deodorized,polyether-modified polysiloxane composition, wherein apolyether-modified polysiloxane composition, synthesized byhydrosilylation in which a polyoxyalkylene having the carbon-carbondouble bond at the terminal is reacted with an organohydrogenpolysiloxane, is refined in the presence of a solid acid. Some of thepreferred embodiments are described below.

-   (1) The deodorized, polyether-modified polysiloxane composition of    the 11^(th) aspect, wherein the polyether-modified polysiloxane    composition is represented by the general formula (2).-   (2) The method of the 13^(th) aspect for producing a deodorized,    polyether-modified polysiloxane composition, wherein water is    incorporated in the treatment in the presence of a solid acid.-   (3) The method of the 15^(th) aspect for producing a deodorized,    polyether-modified polysiloxane composition, wherein the treatment    in the presence of a solid acid is carried out after the    hydrogenation of the polyether-modified polysiloxane composition.-   (4) The method of the 15^(th) aspect for producing a deodorized,    polyether-modified polysiloxane composition, wherein the treatment    in the presence of a solid acid is carried out before the    hydrogenation of the polyether-modified polysiloxane composition.-   (5) The method of the 18^(th) aspect for producing a deodorized,    polyether-modified polysiloxane composition, wherein the solid acid    is solid, acidic zirconium oxide.-   (6) The method of the 18^(th) aspect for producing a deodorized,    polyether-modified polysiloxane composition, wherein the solid acid    is strongly acidic cation-exchanging resin.

DETAILED DESCRIPTION OF THE INVENTION

The deodorized, polyether-modified polysiloxane composition, method forproducing the same and cosmetic containing the same of the presentinvention are described in more detail for each item.

The deodorized, polyether-modified polysiloxane composition of thepresent invention is a polyether-modified polysiloxane composition,synthesized by hydrosilylation in which a polyoxyalkylene having thecarbon-carbon double bond at the terminal is reacted with anorganohydrogen polysiloxane, refined in the presence of a solid acid.

1. Polyether-modified Polysiloxane Composition

The organohydrogen polysiloxanes for forming the polyether-modifiedpolysiloxane composition for the present invention by hydrosilylationinclude a compound represented by the following formula:R¹ ₃SiO(R¹ ₂SiO)_(n)SiR¹ ₃[wherein, R¹s are each a substituted or unsubstituted monovalenthydrocarbon group (e.g., alkyl of 1 to 19 carbon atoms (e.g., methyl orethyl), phenyl, alkylphenyl, naphthyl, alkylnaphthyl or phenylalkylgroup, or 3-aminopropyl, 3-(N-2-aminoethylamino)propyl or3,3,3-trifluoropropyl group, which may be the same or different, grouprepresented by the following formula:—O—(R² ₂SiO)_(q)SiR² ₃[wherein, R²s are each a substituted or unsubstituted monovalenthydrocarbon group (e.g., alkyl (e.g., methyl or ethyl), phenyl,alkylphenyl or phenylalkyl group of 1 to 19 carbon atoms, or3-aminopropyl, 3-(N-2-aminoethylamino)propyl or 3,3,3-trifluoropropylgroup, which may be the same or different, or hydrogen atom; and “q” is0 or a positive integer], or hydrogen atom; and “n” is 0 or positiveinteger, where there is at least one hydrogen atom directly bound to thesilicon atom in the molecule, or group represented by the followingformula:

(wherein, R¹ is the same as the above; and “m” is an integer of 3 ormore, where there is at least one hydrogen atom directly bound to thesilicon atom in the molecule].

These organohydrogen polysiloxanes may be used either individually or incombination.

The polyoxyalkylenes for forming the polyether-modified polysiloxanecomposition by hydrosilylation include a compound represented by thefollowing formula:R′O(R″O)_(x)R′[wherein, R′s are each a substituted or unsubstituted monovalentunsaturated hydrocarbon group (e.g., allyl, methallyl or 3-butenylgroup, or an alkyl, phenyl, alkylphenyl, naphthyl or alkylnaphthyl of 1to 19 carbon atoms), acyl group or hydrogen atom, which may be the sameor different; R″s are each a substituted or unsubstituted divalenthydrocarbon group (e.g., ethylene, propylene or butylenes); and “x” is 0or positive integer, where at least one R′ in the molecule is ahydrocarbon group having an unsaturated substituent].

These polyoxyalkylenes may be used either individually or incombination.

The hydrosilylation can be carried out by a known process. For example,it may be carried out in the presence or absence of solvent, and thesolvent, when used, may be selected from organic solvents, e.g., the onebased on alcohol (e.g., ethanol or isopropyl alcohol), aromatichydrocarbon (toluene or xylene), ether (e.g., dioxane or THF), aliphatichydrocarbon and chlorinated hydrocarbon.

The hydrosilylation may be carried out in the absence of catalyst, butpreferably in the presence of catalyst to reduce reaction temperatureand/or reaction time. The hydrosilylation catalysts useful for thepresent invention include platinum, ruthenium, rhodium, palladium,osmium and iridium compounds, of which platinum compounds areparticularly preferable for their high catalytic activity. The platinumcompounds include chloroplatinate; metallic platinum; metallic platinumcarried by alumina, silica, carbon black or the like; and platinumcomplexes, e.g., platinum/vinyl siloxane, platinum/phosphine andplatinum/alcolate. The platinum catalyst, when used, is incorporated inthe system at 0.0001 to 0.1% by weight as metallic platinum.

The hydrosilylation is normally carried out at 50 to 150° C. for 10minutes to 24 hours, preferably 1 to 10 hours.

The reaction system normally contains an excessive quantity of thepolyoxyalkylene.

The examples of the polyether-modified polysiloxane composition producedby the hydrosilylation include those represented by the general formula(1):R¹ ₃SiO(R₂SiO)_(m)(RXSiO)_(n)SiR¹ ₃  (1)(wherein, Rs are each hydrogen atom, or a substituted or unsubstitutedmonovalent hydrocarbon group; “m” is 0 or a positive integer and “n” is0 or a positive integer; and X is a group represented by the generalformula:—C_(x)H_(2x)(OC₂H₄)_(y)(OC₃H₆)_(z)OA(wherein, A is hydrogen atom, or a group selected from the groupconsisting of a monovalent hydrocarbon group or one represented by theformula R²—(CO)— (R² is a monovalent hydrocarbon group); “x” is aninteger of 2 to 15, “y” is an integer of 0 to 100 and “z” is an integerof 0 to 100, “y+z” being an integer of 100 or less; and R¹ is a groupselected from the group consisting of R and X, at least one of R¹s beingX when “n” is 0), or the general formula (2):[(R₂SiO)_(m)R₂SiC_(x)H_(2x)(OC₂H₄)_(y)(OC₃H₆)_(z)OC_(x)H_(2x)]_(p)  (2)(wherein, Rs are each hydrogen atom, or a substituted or unsubstitutedmonovalent hydrocarbon group; “m” is a positive integer and “p” is aninteger of 1 to 100, “x” is an integer of 2 to 15, “y” is an integer of0 to 100 and “z” is an integer of 0 to 100, “y+z” being an integer of100 or less).2. Refining of the Polyether-modified Polysiloxane Composition

The normal polyether-modified polysiloxane composition is refined bydistilling off the solvent from the hydrosilylation effluent. Therefore,the unreacted polyoxyalkylene remains in the polyether-modifiedpolysiloxane composition. An allyl-etherified polyoxyalkylene may causeisomerization in the presence of a catalyst, e.g., platinum catalyst.For example, hydrosilylation of a polyoxyalkylene allyl-etherified atthe terminal produces a propenyl-etherified polyoxyalkylene at aconstant rate. As a result, a propenyl-etherified polyoxyalkylene andpolyoxyalkylene allyl-etherified at the terminal remain in thepolyether-modified polysiloxane composition contains.

The propenyl-etherified polyoxyalkylene is a vinyl ether type compound,and is easily hydrolyzed to produce a lighter product. In other words,the propenyl-etherified polyoxyalkylene is gradually hydrolyzed in thepresence of moisture in air and only a small quantity of acid to producepropionaldehyde, which gives off a foul odor.

An unreacted polyoxyalkylene allyl-etherified at the terminal isgradually transformed into the propenyl-etherified polyoxyalkylene bythe action of a platinum catalyst remaining in the polyether-modifiedpolysiloxane composition or deteriorated by oxidation proceeding withthe lapse of time, to give off a foul odor. Moreover, a polyoxyalkyleneallyl-etherified at the terminal is itself less stable to oxidation thana normal saturated hydrocarbon, and the resulting oxide can cause a foulodor. When a vinyl silane type compound is produced as a by-product ofthe hydrosilylation, it is considered to be low in stability tooxidation. It is therefore necessary to remove a propenyl-etherifiedpolyoxyalkylene and, at the same time, not to allow a compoundstructurally unstable to cause a foul odor to remain in thepolyether-modified polysiloxane composition, in order to produce thecomposition stable with time to cause no foul odor by hydrolysis oroxidation.

The deodorized, polyether-modified polysiloxane composition of thepresent invention is a polyether-modified polysiloxane composition,synthesized by hydrosilylation, refined in the presence of a solid acid.The refining process preferably includes treatment by the hydrogenationdescribed below. When coupled with the hydrogenation, the treatment inthe presence of a solid acid refines the polyether-modified polysiloxanecomposition to a still higher extent.

The treatment in the presence of a solid acid may come before or afterthe hydrogenation.

(1) Treatment by Hydrogenation

First, the treatment by hydrogenation is described.

The treatment by hydrogenation is carried out to hydrogenate a compoundhaving an unsaturated substituent, e.g., carbon-carbon double bond, andcompound produced by hydrolysis or oxidation, and thereby to produce therefined polyether-modified polysiloxane composition.

A known hydrogenation catalyst, e.g., nickel, palladium, platinum,rhodium, cobalt, chromium, copper or iron in the form of element orcompound is used for the treatment. The catalyst carrier is notessential. When used, it is of activated carbon, silica, silica-alumina,alumina, zeolite or the like. The platinum catalyst for thehydrosilylation can be directly used. These catalysts may be used eitherindividually or in combination.

The hydrosilylation can be carried out in the presence or absence ofsolvent, and the solvent, when used, may be selected from thoseunreactive under the hydrogenation conditions, e.g., the one based onalcohol (e.g., ethanol or isopropyl alcohol), aromatic hydrocarbon(toluene or xylene), ether (e.g., dioxane or THF), aliphatichydrocarbon, chlorinated hydrocarbon and water. The solvent for thehydrosilylation can be directly used. These solvents may be used eitherindividually or in combination.

The hydrogenation may be carried out at normal or elevated pressure, inactuality at an elevated pressure of 1 to 200 Kg/cm² in a hydrogenatmosphere. Hydrogenation temperature is 0 to 200° C., preferably 50 to170° C. to shorten reaction time.

The hydrogenation process may be batchwise or continuous. For thebatchwise process, reaction time is around 3 to 12 hours, althoughvarying depending on conditions, e.g., catalyst quantity andtemperature.

In the batchwise process, the hydrogenation reaction may be terminated 1to 2 hours after the hydrogen pressure shows essentially no decrease.However, it is preferable to keep pressure at a high level by making uphydrogen for shortening reaction time, when it decreases during thereaction process.

The hydrogenation effluent is filtered by diatomaceous earth oractivated carbon under a pressure with nitrogen, to separate thecatalyst for the hydrosilylation and hydrogenation.

When a solvent is used for the reaction, or a lighter fraction ispresent in the hydrogenation effluent, the polyether-modifiedpolysiloxane composition is refined by distilling off the solvent orlighter fraction, as required, under a vacuum in an atmosphere ofnitrogen blown into the system. Removal of the lighter fraction may becarried out as a pretreatment step for the hydrogenation, or twicebefore and after the hydrogenation.

The hydrogenation treatment can deodorize the polyether-modifiedpolysiloxane composition to some extent, because it removes theunsaturated group from the composition and hence reduces propionaldehydeor the like derived from the unsaturated group.

However, the hydrogenation treatment alone may allow an aldehydecondensate, e.g., acetal, to remain in the composition, as discussedabove. It may be transformed into aldehyde in an aqueous solution tocause a foul odor. This is because the hydrogenation treatment alonecannot remove an aldehyde condensate, which contains no unsaturatedbond, and hence a substance which causes a foul odor will still remainin the hydrogenation effluent.

(2) Treatment in the Presence of a Solid Acid

The present invention treats the polyether-modified siloxane compositionin the presence of a solid acid in combination with the treatment byhydrogenation described above, which cannot completely remove analdehyde condensate, e.g., acetal. The treatment in the presence of asolid acid can deodorize the composition by decomposing the aldehydecondensate remaining therein, i.e., can produce a deodorizedpolyether-modified siloxane composition.

As described above, the treatment in the presence of a solid acid maycome before the hydrogenation. In this case, a propenyl-etherifiedpolyoxyalkylene and aldehyde condensate, e.g., acetal, are decomposed inthe presence of a solid acid, and the aldehyde produced, residualalkenylated polyoxyalkylene and the like are reduced by thehydrogenation. This process can also deodorize the polyether-modifiedsiloxane composition.

Moreover, the present invention can depend only on the treatment in thepresence of a solid acid, which can decompose an aldehyde condensate,e.g., acetal, in addition to a propenyl-etherified polyoxyalkylene, asdiscussed above, and hence deodorize the polyether-modified siloxanecomposition.

The treatment in the presence of a solid acid for the present inventionmeans a decomposition treatment in which the polyether-modified siloxanecomposition synthesized by the hydrosilylation is stirred together witha solid acid in a reaction system (e.g., flask or other reactors), orhydrolysis treatment in which it is stirred together with a solid acidand water or solid acid, water and organic solvent, although not limitedthereto. The hydrolysis treatment with stirring in the presence of asolid acid and water is particularly preferable. It is preferablycarried out under the conditions of 0 to 200° C., more preferably 80 to100° C., for around 0.5 to 24 hours, more preferably 1 to 10 hours.

Alternately, the polyether-modified siloxane composition synthesized bythe hydrosilylation may be passed (flown) in a reactor packed with asolid acid. In this case, the reaction is carried out at 0 to 200° C.,preferably 80 to 100° C., for around 0.5 to 24 hours, preferably around1 to 10 hours, with recycling.

When a lighter fraction is present in the reaction system, it ispreferable to refine the polyether-modified polysiloxane composition bydistilling off the lighter fraction, as required, under a vacuum in anatmosphere of nitrogen blown into the system while the composition istreated in the presence of a solid acid. Removal of the lighter fractionmay be carried out as a pretreatment or post treatment step for thetreatment in the presence of a solid acid, or twice before and after thetreatment in the presence of a solid acid.

In the present invention, the treatment in the presence of a solid acidcan be preferably carried out in the presence of water, as discussedabove. A water-soluble organic solvent may be used in combination withwater, when the polyether-modified polysiloxane composition is sparinglysoluble in water. The organic solvents useful for the present inventioninclude a saturated, monovalent alcohol of 1 to 5 carbon atoms, THF,dioxane and acetone.

The solid acid is an acidic solid. The present invention uses at leastone type of a solid acid selected from the group consisting of solid,acidic zirconium oxide (or solid, acidic zirconia), strongly acidiccation-exchanging resin, fluorinated sulfonic acid resin, acidic clay,alumina, silica-alumina and zeolite. It is preferably solid, acidiczirconium oxide or strongly acidic cation-exchanging resin, the formerbeing more preferable.

More specifically, the solid, acidic zirconium oxide is prepared bytreating zirconium hydroxide with sulfuric acid and then heating at 300°C. or higher. Still more specifically, the solid, acidic zirconiumoxide, e.g., zirconia sulfate, can be prepared by a process comprisingsteps of kneading aluminum hydroxide and/or hydrous oxide, zirconiumhydroxide and/or hydrous oxide and a compound containing sulfuric acid;forming the above mixture; and firing the formed product at atemperature, more specifically 300° C. or higher, at which zirconia ofthe tetragonal structure is produced. The commercial products include“SZA-60” supplied by Japan Energy as a solid, acidic zirconium catalyst.

The strongly acidic cation-exchanging resins include the one having asulfonic acid group (—SO₃H) as a functional group. The commercialproducts include Amberlists 15, 16, 31 and 35 (US's Rhom and Haas,supplied by Organo). The fluorinated sulfonic acid resin is aperfluorinated polymer having a sulfonic acid group bound to andsuspended from the polymer chain. It is specifically disclosed by, e.g.,JP-B-59-4446.

The treatment in the presence of a solid acid allows no acid to remainin the system. It disperses with a neutralization step, and allows noneutralization salt to remain in the system. When treated in thepresence of a solid acid, therefore, the polyether-modified polysiloxanecomposition is free from deterioration resulting from a residual acidicsubstance or neutralization salt with the lapse of time, morespecifically resulting from oxidation of the composition in the presenceof a residual acid, or depolymerization or polymerization of thecomposition in the presence of a residual neutralization salt. Thecomposition containing no residual acid or neutralization salt hasanother advantage that the hydrogenation reaction, when carried outafter the treatment in the presence of a solid acid, is not retarded bythe residual acid or salt. Still another advantage is that thecomposition gives off no foul odor caused by the residual acid or saltby itself or its decomposition.

The deodorized, polyether-modified polysiloxane composition may beincorporated, after being refined, with an antioxidant, e.g., one basedon phenol, hydroquinone, benzoquinone, aromatic amine or vitamin, tohave improved stability against oxidation.

The antioxidants useful for the present invention include2,6-di-t-butyl-p-cresol (BHT), and vitamins C and E. It is incorporatedat 10 to 1000 ppm based on the deodorized, polyether-modifiedpolysiloxane composition after it is refined, preferably 50 to 500 ppm.

It may be incorporated before the step of distilling off the lighterfraction.

The deodorized, polyether-modified polysiloxane composition of thepresent invention can be used for various purposes. In particular, itcan go into cosmetics, centered by the perfume-free ones for the skinand hair, for which the conventional polyether-modified polysiloxanecomposition is difficult to use for its foul odor.

When used for a cosmetic, the deodorized, polyether-modifiedpolysiloxane composition of the present invention is incorporatedpreferably at around 0.1 to 40% by weight based on the whole cosmetic.Moreover, it may be incorporated with any known component normally usedfor cosmetics within limits not harmful to the effect of the presentinvention.

For hair cosmetics, for example, it may be incorporated with any knowncomponent normally used within limits not harmful to the effect of thepresent invention. More specifically, these components include siliconecompounds in the form of oil, resin, gum, rubber, powder or the like[e.g., dimethyl polysiloxane, dimethyl methylphenyl polysiloxane,amino-modified dimethyl polysiloxane, epoxy-modified dimethylpolysiloxane and polycaprolactone-modified dimethyl polysiloxane];various oils [camellia oil, rapeseed oil, sesame oil, safflower oil,cotton oil, castor oil, soybean oil, copra oil, palm oil, beeswax,montan wax, lanoline and squalene]; surfactants [e.g., alkyl benzenesulfonate, polyoxyalkylene alkyl benzene sulfuric acid ester, alkylsulfuric acid ester, alkane sulfonate, alkyl ethoxy carboxylate,succinic acid derivative, alkyl amine oxide, imidazoline type compound,polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkylphenylether, and higher fatty acid alkanol amide and alkylene oxide adductthereof]; high-molecular-weight compounds [e.g., hydroxyethyl cellulose,hydroxypropyl cellulose, hydroxypropylmethyl cellulose, methylcellulose, cationized cellulose, cationized high-molecular-weightcompound, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetatecopolymer, vinyl pyrrolidone/vinyl acetate/alkylaminoacrylate copolymer,lower alkyl half-ester of methylvinyl ether/maleic anhydride copolymer,vinyl acetate/crotonic acid copolymer, acrylic acid/acrylic acidester/N-alkyl acrylamide copolymer, vinyl acetate/crotonicacid/vinyl-tert-butyl benzoate copolymer, poly(2-acrylamide-2-sodiummethyl propane sulfonate), vinyl pyrrolidone/methacrylic acid/aceticacid (tert-butyl) copolymer and vinyl pyrrolidone/acrylic acid (ormethacrylic acid) copolymer; amino acids [e.g., glycine, serine andproline]; powders [e.g., sericite, silica-alumina, silica gel, kaolin,talc, colcothar, ultramarine blue, mica, mica titanium, iron oxide,titanium oxide, magnesium oxide, chromium oxide, antimony oxide, zincmonoxide, zinc dioxide, magnesium carbonate, calcium carbonate, calciumphosphate, barium sulfate, aluminum hydroxide, chromium hydroxide,magnesium aluminometasilicate, magnesium aluminosilicate andpolyethylene]; and antioxidants, ultraviolet absorbers, humectants,perfumes, dyes, pigments, colorants, preservatives, vitaminpreparations, hormone preparations, deodorants, sticking agents andanti-inflammatory agents.

EXAMPLES

The present invention is described by EXAMPLES and COMPARATIVE EXAMPLES,which by no means limit the present invention.

Example 1 Synthesis and Refining Polyether-modified Polysiloxane 1

A 1000 mL (1 L) four-mouthed flask equipped with a stirrer, refluxcondenser, thermometer and nitrogen inlet port was charged with 240 g ofmethyl hydrogen polysiloxane (hydrogen generation rate: 93.51 mL/g,structural formula: (CH₃)₃SiO[(CH₃)₂SiO]₁₀[(CH₃)HSiO]₅Si(CH₃)₃ and 666.7g of allyl polyether (structural formula: CH₂═CHCH₂O(C₂H₄O)₁₀CH₃, towhich a toluene solution of platinum divinyltetramethyl disiloxane(platinum concentration: 3.0% by weight) was added for the reaction at80° C. for 2 hours.

The effluent was hydrolyzed at 95° C. for 5 hours in the presence of 1.3g of zirconia sulfate (Japan Energy, SZA-60) and 9 g of refined water.The effluent was treated by vacuum distillation to remove the lighterfraction and then by filtration to prepare Polyether-modifiedPolysiloxane 1.

Polyether-modified Polysiloxane 1 is structurally represented by thegeneral formula (1), wherein R═R¹═A═CH₃, “m”=10, “n”=5, “x”=3, “y”=10and “z”=0, i.e.,(CH₃)₃SiO[(CH₃)₂SiO]₁₀[(CH₃)(C₃H₆O(C₂H₄O)₁₀CH₃)SiO]₅Si(CH₃)₃.

Example 2 Polyether-modified Polysiloxane 2

In this example, 700 g of Polyether-modified Polysiloxane 1 prepared inEXAMPLE 1 was hydrogenated in an autoclave with hydrogen at 140° C. and80 kg/cm² for 6 hours in the presence of 35 g of Raney nickel. Theeffluent was treated by filtration to remove the catalyst, by vacuumdistillation to remove the lighter fraction and then by filtration toprepare Polyether-modified Polysiloxane 2.

Example 3 Synthesis and Refining Polyether-modified Polysiloxane 3

A 1 L four-mouthed flask equipped with a stirrer, reflux condenser,thermometer and nitrogen inlet port was charged with 240 g of methylhydrogen polysiloxane (hydrogen generation rate: 93.51 mL/g, structuralformula: (CH₃)₃SiO[(CH₃)₂SiO]₁₀[(CH₃)HSiO]₅Si(CH₃)₃ and 666.7 g of allylpolyether (structural formula: CH₂═CHCH₂O(C₂H₄O)₁₀CH₃, to which a 10%ethanol solution of chloroplatinic acid was added for the reaction at 80to 100° C. for 2 hours.

The effluent was neutralized with sodium bicarbonate, and treated byvacuum distillation at 90 to 100° C. to remove the lighter fraction andthen by filtration.

In this example, 700 g of the filtrate prepared above was hydrogenatedin an autoclave with hydrogen at 140° C. and 80 kg/cm² for 6 hours inthe presence of 35 g of Raney nickel. The effluent was treated byfiltration to remove the catalyst, hydrolyzed at 95° C. for 5 hours inthe presence of 1 g of zirconia sulfate (Japan Energy, SZA-60) and 6 gof refined water. The effluent was treated by vacuum distillation toremove the lighter fraction and then by filtration to preparePolyether-modified Polysiloxane 3.

Polyether-modified Polysiloxane 3 was structurally the same asPolyether-modified Polysiloxane 1.

Example 4 Synthesis and Refining Polyether-modified Polysiloxane 4

A 1 L four-mouthed flask equipped with a stirrer, reflux condenser,thermometer and nitrogen inlet port was charged with 240 g of methylhydrogen polysiloxane (hydrogen generation rate: 93.51 mL/g, structuralformula: (CH₃)₃SiO[(CH₃)₂SiO]₁₀[(CH₃)HSiO]₅Si(CH₃)₃ and 666.7 g of allylpolyether (structural formula: CH₂═CHCH₂O(C₂H₄O)₁₀CH₃, to which a 10%ethanol solution of chloroplatinic acid was added for the reaction at 80to 100° C. for 2 hours.

The effluent was neutralized with sodium bicarbonate, and treated byvacuum distillation at 90 to 100° C. to remove the lighter fraction andthen by filtration.

In this example, 700 g of the filtrate prepared above was hydrogenatedin an autoclave with hydrogen at 140° C. and 80 kg/cm² for 6 hours inthe presence of 35 g of Raney nickel. The effluent was treated byfiltration to remove the catalyst.

The filtrate was also hydrolyzed by another flow system comprising apump, reactor tower (inner diameter: 15 mm) equipped with a furnace and500 mL, four-mouthed flask equipped with a magnetic stirrer connected inthis order, where the reactor tower was packed with 20 mL of zirconiasulfate (Japan Energy, SZA-60) and sealed with glass wool at both ends.The zirconia sulfate was moderately crushed by a mortar beforehand tohave a uniform size of 10 to 20 meshes and fired at 350° C. for 2 hoursin an oven immediately before the test.

A mixture of 300 mL of the filtrate prepared above and 3 g of refinedwater, put in the four-mouthed flask, was flown with stirring throughthe reaction system kept at 100° C. for 6 hours, where the effluent wastreated by vacuum distillation to remove the lower-boiling-pointfraction and then recycled back to the reactor tower to preparePolyether-modified Polysiloxane 4.

Polyether-modified Polysiloxane 4 was structurally the same asPolyether-modified Polysiloxane 1.

Example 5 Polyether-modified Polysiloxane 5

Polyether-modified Polysiloxane 5 was prepared in the same manner as inEXAMPLE 3, except that zirconia sulfate was replaced by a stronglyacidic cation-exchanging resin (Organo, Amberlist 35).

Comparative Example 1

Comparative Sample 1 was prepared in the same manner as in EXAMPLE 1,except that the effluent was not treated with zirconia sulfate, andtreated by vacuum distillation, after it was incorporated with 2.5 g ofsodium bicarbonate, to remove the lighter fraction and then byfiltration.

Comparative Example 2

Comparative Sample 2 was prepared in the same manner as in EXAMPLE 1,except that the effluent was hydrolyzed with 9 g of 0.1 mols/Lhydrochloric acid in place of zirconia sulfate at 95° C. for 1 hour, andtreated by vacuum distillation, after it was incorporated with 4.5 g ofsodium bicarbonate for neutralization, to remove the lighter fractionand then by filtration.

Comparative Example 3

Comparative Sample 3 was prepared in the same manner as in EXAMPLE 2,except that the effluent was not treated with zirconia sulfate.

Comparative Example 4

In this comparative example, 700 g of Comparative Sample 1 prepared inCOMPARATIVE EXAMPLE 1 was hydrogenated in an autoclave with hydrogen at140° C. and 80 kg/cm² for 6 hours in the presence of 35 g of Raneynickel, after it was incorporated with 3.5 g of a phosphoric acid-basedbuffer solution comprising phosphoric acid, citric acid and sodiumhydroxide, adjusted at a pH of 3.3. The effluent was treated byfiltration to remove the catalyst, by vacuum distillation to remove thelighter fraction and then by filtration to prepare Comparative Sample 4.

Comparative Example 5

Comparative Sample 5 was prepared in the same manner as in EXAMPLE 3,except that the effluent was hydrolyzed with 7 g of 0.1 mols/Lhydrochloric acid in place of zirconia sulfate at 95° C. for 1 hour, andtreated by vacuum distillation, after it was neutralized with 3.5 g ofsodium bicarbonate, to remove the lighter fraction and then byfiltration.

Comparative Example 6

In this comparative example, 700 g of Comparative Sample 2 prepared inCOMPARATIVE EXAMPLE 2 was hydrogenated in an autoclave with hydrogen at140° C. and 80 kg/cm² for 6 hours in the presence of 35 g of Raneynickel, as was the case with EXAMPLE 2. The effluent was treated byfiltration to remove the catalyst, by vacuum distillation to remove thelighter fraction and then by filtration to prepare Comparative Sample 6.

The polyether-modified polysiloxanes prepared in EXAMPLES 1 to 5 andCOMPARATIVE EXAMPLES 1 to 6 were evaluated for their odor, and changedviscosity and pH level.

For evaluation of the odor, the sample itself was observed immediatelyafter it was prepared and after it was kept at 70° C. for 1 month. Atthe same time, a mixture of 3 g of the sample, 3 g of propylene glycoland 24 g of refined water was also observed immediately after it wasprepared and after it was kept at 70° C. for 2 weeks for evaluating thecompounded system.

They were evaluated according to the following standards:

-   -   No odor is given off. ⊚    -   Little odor is given off. ◯    -   Odor is given off slightly. Δ    -   Odor is given off strongly. ×

For evaluation of changed viscosity, the sample was observed immediatelyafter it was prepared and after it was kept at 70° C. for 1 month.

For evaluation of changed pH level, the sample was observed immediatelyafter it was prepared and after it was kept at 25° C. for 1 month, whereit was dissolved in refined water to be tested at 25° C. as a 10% byweight aqueous solution.

The results are summarized in Table 1. As shown, it was confirmed thatthe deodorized, polyether-modified polysiloxane composition(polyether-modified polysiloxane) of the present invention has notableeffects with respect to odor, and changed viscosity and pH level.

TABLE 1 Odor Changed pH level Sample itself Compounded system pH AfterAfter Changed After EXAMPLES/ elapse of elapse of viscosity elapse ofCOMPARATIVE Initial specific Initial specific Change rate specificEXAMPLES Refining treatment stage time stage time (%) Initial stage timeEXAMPLE 1 Solid acid ⊚ ◯ ⊚ ◯~Δ Less than 1% 6.8 6.3 (zirconia sulfate)EXAMPLE 2 Solid acid and ⊚ ⊚ ⊚ ⊚ Less than 1% 7.0 6.8 hydrogenationEXAMPLE 3 Hydrogenation ⊚ ⊚ ⊚ ⊚ Less than 1% 6.8 6.5 and solid acidEXAMPLE 4 Fixed bed ⊚ ⊚ ⊚ ⊚ Less than 1% 6.9 6.5 (zirconia sulfate)EXAMPLE 5 Strongly acidic, ⊚ ⊚ ⊚ ⊚ Less than 1% 6.9 6.6cation-exchanging resin COMPARATIVE Blank X X X X Increased by 5% 5.94.3 EXAMPLE 1 COMPARATIVE Treatment with Δ X Δ X Increased by 10% 5.43.2 EXAMPLE 2 hydrochloric acid COMPARATIVE Hydrogenation only ⊚ ◯ ⊚ ΔLess than 1% 6.9 6.4 EXAMPLE 3 COMPARATIVE Hydrogenation in the ◯ X Δ XIncreased by 7% 5.8 4.8 EXAMPLE 4 presence of a buffer solution ofphosphoric acid COMPARATIVE Hydrogenation ⊚ ◯ ⊚ ◯~Δ Increased by 5% 6.15.7 EXAMPLE 5 and treatment with hydrochloric acid COMPARATIVE Treatmentwith ⊚ ◯ ⊚ ◯~Δ Increased by 3% 6.3 5.3 EXAMPLE 6 hydrochloric acid andhydrogenation

The deodorized, polyether-modified polysiloxane composition of thepresent invention is of a polyether-modified polysiloxane composition,synthesized by hydrosilylation in which a polyoxyalkylene having thecarbon-carbon double bond at the terminal is reacted with anorganohydrogen polysiloxane, and is highly refined by treatment in thepresence of a solid acid, exhibiting notable effects of not producing asubstance giving off a foul odor, while being produced or stored, whichresults from hydrolysis, oxidation or the like of a by-product orunreacted material and of being temporarily stable.

Therefore, it can go into cosmetics, centered by the perfume-free onesfor the skin and hair, for which the conventional polyether-modifiedpolysiloxane composition is difficult to use for its foul odor.

1. A method for producing a deodorized, polyether-modified polysiloxanecomposition, comprising a step of treating a polyether-modifiedpolysiloxane composition, synthesized by hydrosilylation in which apolyoxyalkylene having the carbon-carbon double bond at the terminal isreacted with an organohydrogen polysiloxane, in the presence of a solidacid, being a member selected from the group consisting of solid, acidiczirconium oxide, strongly acidic cation-exchanging resin, fluorinatedsulfonic acid resin, and acidic clay, by combining the polysiloxanecomposition, said solid acid and one or more members selected from thegroup consisting of water and organic solvent.
 2. The method accordingto claim 1 for producing a deodorized, polyether-modified polysiloxanecomposition, comprising a step of hydrogenation of thepolyether-modified polysiloxane composition, in addition to thetreatment in the presence of a solid acid.
 3. The method according toclaim 2 for producing a deodorized, polyether-modified polysiloxanecomposition, wherein the treatment in the presence of a solid acid iscarried out before or after the hydrogenation of the polyether-modifiedpolysiloxane composition.
 4. The method according to claim 1 forproducing a deodorized, polyether-modified polysiloxane composition,wherein a step for distilling off a lighter fraction is carried outduring or after the treatment in the presence of a solid acid, or beforeor after the treatment by hydrogenation.
 5. The method according toclaim 1 for producing a deodorized, polyether-modified polysiloxanecomposition, wherein the solid acid is one of solid, acidic zirconiumoxide and strongly acidic cation-exchanging resin.
 6. The methodaccording to claim 1 wherein the polyether-modified polysiloxanecomposition contains at least one selected from the group consisting ofa compound represented by the general formula (1):R¹ ₃SiO(R₂SiO)_(m)(RXSiO)_(n)SiR¹ ₃  (1) wherein, Rs are each hydrogenatom, or a substituted or unsubstituted monovalent hydrocarbon group;“m” is 0 or a positive integer and “n” is 0 or a positive integer; and Xis a group represented by the general formula:—C_(x)H_(2x)(OC₂H₄)_(y)(OC₃H₆)_(z)OA wherein, A is hydrogen atom, or agroup selected from the group consisting of a monovalent hydrocarbongroup or one represented by the formula R²—(CO)—(R² is a monovalenthydrocarbon group; “X” is an integer of 2 to 15, “y” is an integer of 0to 100 and “z” is an integer of 0 to 100, “y+z” being an integer of 100or less; and R′ is a group selected from the group consisting of R andX, at least one of R′s being X when “n” is 0, and a compound representedby the general formula (2):[(R₂SiO)_(m)R₂SiC_(x)H_(2x)(OC₂H₄)_(y)(OC₃H₆)_(z)OC_(x)H_(2x)]_(p)  (2)wherein, Rs are each hydrogen atom, or a substituted or unsubstitutedmonovalent hydrocarbon group; “m” is a positive integer and “p” is aninteger of 1 to 100, “x” is an integer of 2 to 15, “y” is an integer of0 to 100 and “Z” is an integer of 0 to 100, “y+z” being an integer of100 or less.
 7. The method according to claim 1 for producing adeodorized, polyether-modified polysiloxane composition, wherein thetreating is hydrolysis treating.
 8. The method according to claim 7 forproducing a deodorized, polyether-modified polysiloxane composition,wherein the hydrolysis treating is carried out under conditions of 0 to200° C. for around 0.5 to 24 hours.
 9. The method according to claim 7for producing a deodorized, polyether-modified polysiloxane composition,wherein the hydrolysis treating is carried out under conditions of 80 to100° C. for around 1 to 10 hours.
 10. The method according to claim 1for producing a deodorized, polyether-modified polysiloxane composition,wherein the organic solvents are selected from the group consisting ofsaturated, monovalent alcohol of 1 to 5 carbon atoms, THF, dioxane andacetone.
 11. The method according to claim 1 for producing a deodorized,polyether-modified polysiloxane composition, further comprising the stepof incorporating with an antioxidant selected from the group consistingof 2,6-di-t-butyl-p-cresol (BHT), vitamin C and vitamin E.
 12. Themethod according to claim 11 for producing a deodorized,polyether-modified polysiloxane composition, wherein the antioxidant isincorporated at 10 to 1000 ppm based on the deodorized,polyether-modified polysiloxane composition after it is refined.
 13. Themethod according to claim 11 for producing a deodorized,polyether-modified polysiloxane composition, wherein the antioxidant isincorporated at 50 to 500 ppm based on the deodorized,polyether-modified polysiloxane composition after it is refined.